CN101816957B - Photochemical preparation method of phyllosilicate loaded metal sulphide photocatalyst - Google Patents
Photochemical preparation method of phyllosilicate loaded metal sulphide photocatalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a loaded photocatalyst, and particularly discloses a preparation method of a phyllosilicate loaded metal sulphide photocatalyst. The method comprises the following steps of: (1) preparing metal ion exchanged phyllosilicate; (2) preparing a precursor liquid; (3) carrying out a photochemical reaction; and (4) post-treating the photocatalyst. The invention has the advantages of mild conditions of preparation reaction, simple process, no need of high-temperature post-treatment, strong practicability, low equipment requirements, low cost and the like. The prepared phyllosilicate loaded metal sulphide photocatalyst can degrade methyl orange, methylthionine chloride and other organic matters in ultraviolent light, visible light or natural sunlight, is a cheap photocatalyst used for treating organic contaminants and has better application prospects.
Description
Technical field
The present invention relates to a kind of technology of preparing of loaded photocatalyst material, relate in particular to a kind of photochemical method for preparation of phyllosilicate loaded metal sulphide type photochemical catalyst.
Background technology
The phyllosilicate interlayer contains relatively large exchangeable cations, can replace with multiple cationic substance under certain condition, thereby different cationic substances is incorporated into the sheet interlayer of phyllosilicate, realizes the intercalation or the pillared modification of phyllosilicate.Phyllosilicate has obtained broad research and application as a kind of stable performance, aboundresources, cheap carrier material, has become the preferred material of catalyst carrier.At present preparation phyllosilicate supported catalyst agent material majority all is at first by methods such as ion-exchange, dipping, co-precipitation, collosol and gels catalyst precursor to be loaded between phyllosilicate sheet surfaces or the lamella, and the high-temperature process (most temperature are on 300 ℃) by certain hour will load on the structural catalyst precursor of phyllosilicate and be converted into the material with catalysis again.The high-temperature process power consumption in later stage is high, pollutes greatly, and catalyst structure is wayward, the properties of product poor stability.Develop a kind of simpler, convenient, energy-conservation, mode is converted into the material with catalysis with phyllosilicate loaded complex catalyst precursor thing efficiently, is the significant challenge of this field development.
Semiconductor alloy sulfide such as CdS, CuS, SnS, ZnS etc. have excellent photocatalytic performance, aspect treatment of Organic Wastewater good prospects for application are arranged.But how under the relatively mild condition semiconductor alloy sulfide being loaded to preparation phyllosilicate loaded metal sulphide catalyst on the phyllosilicate lamella, this all rarely has report at home and abroad.
Summary of the invention
The object of the present invention is to provide the photochemical method for preparation of a kind of phyllosilicate loaded metal sulfuration photochemical catalyst, its technology gentleness, simple, cost is low, the metal sulfide in this photochemical catalyst loads on the sheet surfaces of phyllosilicate with the nanometer state.
The objective of the invention is to be achieved through the following technical solutions:
The photochemical method for preparation of phyllosilicate loaded metal sulphide photocatalyst is characterized in that, this method may further comprise the steps:
(1) preparation metal ion exchanged phyllosilicate: phyllosilicate is scattered in the aqueous solution of metalline, stirred 2～6 hours down at 40～80 ℃, in swelling, carry out metal ion exchanged, phyllosilicate after the exchange is separated, washs, obtain the metal ion exchanged phyllosilicate;
(2) preparation precursor liquid: the described metal ion exchanged phyllosilicate that will make is distributed to the precursor liquid that is mixed with phyllosilicate loaded metal sulphide in the aqueous solution that contains the sulphur source;
(3) photochemical reaction: the precursor liquid of the phyllosilicate loaded metal sulphide that makes is positioned under the ultraviolet source stirring reaction 4～48 hours;
(4) post processing of photochemical catalyst: after photochemical reaction finishes, after filtration, promptly get phyllosilicate loaded metal sulphide photocatalyst after the washing, drying.
Further, step (1) is specially:
Phyllosilicate is distributed in the deionized water, compound concentration is the laminar silicic acid salt suspensioning liquid of 1.0～100g/L, the ion exchange capacity of pressing phyllosilicate adds slaine, under 40～80 ℃ temperature, stirred 2～6 hours, in swelling, carry out ion-exchange, phyllosilicate after the exchange is separated, washs, obtain the metal ion exchanged phyllosilicate;
Step (2) is specially:
The above-mentioned metal ion exchanged phyllosilicate that makes is distributed in the deionized water, the consumption of deionized water is 10～100 times of phyllosilicate weight (primary quantity), add the sulphur source then, the sulphur source is (0.1～10) with the ratio of the amount of substance of slaine: 1, stirring and dissolving under room temperature obtains the precursor liquid of phyllosilicate loaded metal sulphide;
Step (3) is specially:
With the precursor liquid of the above-mentioned phyllosilicate loaded metal sulphide that makes be positioned under the ultraviolet source that wavelength is 254～365nm, irradiation intensity is 0.5～5.0mW/cm
2, stirring reaction 4～48 hours.
Further, the described drying of step (4) is 60～90 ℃ of vacuum drying.
Further, layered silicate is selected from imvite, attapulgite, mica and rectorite.
Further, the ion exchange capacity of layered silicate is that 15～110mmol/100g, particle diameter are 10～80 microns.
Further, described slaine is selected from chloride, acetate, nitrate and sulfate.
Further, the metal in the described slaine be selected from copper, cobalt, nickel, every, chromium, zinc, lead, silver, tin and iron.
Further, described sulphur source is solubility thiosulfates such as sodium thiosulfate, potassium thiosulfate, ATS (Ammonium thiosulphate).
The present invention utilizes the switching performance of laminar silicic acid salt pair metal ion, metal ion is loaded on the phyllosilicate sheet surfaces earlier, by photochemical method, form metal sulfide in phyllosilicate sheet surfaces original position, obtain phyllosilicate loaded metal sulphide photocatalyst; Phyllosilicate not only plays loading functional and to the defencive function of metal sulfide, and provides organic adsorption function, and the photo-catalysis function of this loaded photocatalyst is strengthened.This method technology is simple, and a kind of new method for preparing phyllosilicate loaded metal sulphide is provided, and its reaction condition gentleness does not need high-temperature post-treatment, and is pollution-free environmentally friendly, low for equipment requirements.Prepared phyllosilicate loaded metal sulphide photocatalyst is organic matters such as degrade methyl orange, methylene blue under ultraviolet light, visible light or natural sunshine, have application promise in clinical practice as photochemical catalyst aspect the degradable organic pollutant.
The specific embodiment
For ease of understanding, the present invention is further illustrated below in conjunction with specific embodiment, but preparation method of the present invention is not subject to these embodiment.
Embodiment of the present invention provides a kind of photochemical method for preparation of phyllosilicate loaded metal sulphide photocatalyst, utilize laminar silicic acid salt pair metal ion exchanged performance, metal ion is loaded on the phyllosilicate sheet surfaces earlier, by photochemical method, obtain phyllosilicate loaded metal sulphide photocatalyst.Metal sulfide original position between montmorillonite layer generates in this catalyst, is the nanometer distributions.This method for preparing catalyst specifically may further comprise the steps: preparation metal ion exchanged phyllosilicate, make precursor liquid with the aqueous solution in sulfur-bearing source again, carry out light-catalyzed reaction, will obtain phyllosilicate loaded metal sulphide photocatalyst after product filtration, washing, the drying.
Above-mentioned preparation method comprises the steps:
(1) preparation metal ion exchanged phyllosilicate: a certain amount of phyllosilicate is distributed in 100～500ml deionized water, compound concentration is the laminar silicic acid salt suspensioning liquid of 1.0～100g/L, ion exchange capacity by silicate adds a certain amount of slaine, under 40～80 ℃ temperature, stirred 2～6 hours, in swelling, carry out ion-exchange, phyllosilicate after the exchange is separated, washs, obtain the metal ion exchanged phyllosilicate;
(2) preparation phyllosilicate loaded metal sulphide precursor aqueous solution: the described metal ion exchanged phyllosilicate that makes in above-mentioned (1) is scattered in 100～500ml deionized water, compound concentration is the laminar silicic acid salt suspensioning liquid of 1.0～100g/L, the ratio of the amount of metal ion species is (0.1～10) in adding and the metal ion exchanged phyllosilicate: 1 sulphur source material, stirring and dissolving under room temperature obtains the precursor aqueous solution of phyllosilicate loaded metal sulphide;
(3) photochemical reaction: with the precursor aqueous solution of the layered silicate loaded metal sulfide that makes in above-mentioned (2) be positioned under the ultraviolet source that wavelength is 254～365nm, irradiation intensity is 0.5～5.0mW/cm
2, stirring reaction 4～48h;
(4) post processing: the product that makes in above-mentioned (3) is filtered, be washed to no ion and detect, 60～90 ℃ of vacuum constant temperature dryings obtain phyllosilicate loaded metal sulphide photocatalyst.
Above-mentioned phyllosilicate is any one or more in imvite, attapulgite, mica, the rectorite.
Above-mentioned phyllosilicate cation exchange capacity is that 15～110mmol/100g, particle diameter are 10～80 microns.
Above-mentioned slaine be in chloride, acetic acid, nitric acid, the sulfuric acid any or several.
Above-mentioned metal is copper, cobalt, nickel, in, chromium, zinc, lead, silver, tin or iron any or several.
Above-mentioned sulphur source is solubility thiosulfates such as sodium thiosulfate, potassium thiosulfate, ATS (Ammonium thiosulphate).
The preparation method that the embodiment of the invention provides, compared with prior art the present invention has the following advantages:
(1) provides a kind of new method of original position formation nano metal sulphide on the phyllosilicate lamella at normal temperatures;
(2) adopt photochemical method synthetic, utilize the low-power uviol lamp, at room temperature reaction as radiation source, the reaction condition gentleness, pollution-free environmentally friendly, simultaneously owing to do not need follow-up high-temperature calcination, effectively save the energy, reduced the cost of synthesis of nano metal sulfide.
Embodiment 1
Present embodiment provides the preparation method of the CdS-loaded photochemical catalyst of a kind of sodium-based montmorillonite, is to utilize photochemical method to prepare the method for the CdS-loaded photochemical catalyst of phyllosilicate, is specifically undertaken by following step:
The sodium-based montmorillonite and 1.939g eight Cadmium sulfate hydrates (5.5mmol) that take by weighing the 5g average grain diameter respectively and be 10 microns, ion exchange capacity and be 110mmol/100g join in the 100g deionized water, after stirring 6h under 50 ℃, centrifugation, repeatedly washing, drying obtains Cd
2+The exchange imvite; With above-mentioned Cd
2+The exchange imvite is scattered in the 100g deionized water, adds 1.365g hypo (5.5mmol) simultaneously, and stirring and dissolving obtains montmorillonite load CdS precursor liquid; The precursor liquid that obtains is placed irradiation 48h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 2.8mW/cm
2); Product in the precursor liquid reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is dried under 90 ℃ of vacuum, and obtaining product is montmorillonite load CdS photochemical catalyst.For the photocatalysis performance of photochemistry sintetics is described, the commercial P-25 photochemical catalyst of selecting German Deggusa company to produce carries out the photocatalysis contrast experiment, the result shows that commercial P-25 photochemical catalyst can make initial concentration at radiation of visible light after one hour be 10mmol/L methyl orange degradation 71.2%, and the prepared montmorillonite load CdS photochemical catalyst of present embodiment under equal conditions can make methyl orange degradation 83.5% (seeing Table 1).Hence one can see that, and the prepared photochemical catalyst of present embodiment obviously is better than the commercial P-25 photochemical catalyst of using to the photocatalytic activity of methyl orange.
Embodiment 2
Present embodiment provides a kind of preparation method of attapulgite loaded Cu S photochemical catalyst, is to utilize photochemical method to prepare the method for attapulgite loaded Cu S photochemical catalyst, is specifically undertaken by following step:
The attapulgite and the 0.185g copper nitrate (0.9mmol) that take by weighing the 6g average grain diameter respectively and be 80 microns, ion exchange capacity and be 15mmol/100g join in the 200g deionized water, 40 ℃ stir 6h down after, centrifugation, repeatedly washing, drying obtains Cu
2+The exchange attapulgite; With above-mentioned Cu
2+The exchange attapulgite is scattered in the 150g deionized water, adds 0.757g five hydration potassium thiosulfates (2.7mmol) simultaneously, and stirring and dissolving obtains attapulgite loaded Cu S precursor liquid; The precursor aqueous solution that obtains is placed irradiation 24h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 5.0mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is dried under 80 ℃ of vacuum, and obtaining product is attapulgite loaded Cu S photochemical catalyst.
Embodiment 3
Present embodiment provides a kind of preparation method of mica load C oS photochemical catalyst, is to utilize photochemical method to prepare the method for mica load C oS photochemical catalyst, is specifically undertaken by following step:
The mica and the 0.479g CoCL2 (1.8mmol) that take by weighing the 4g average grain diameter respectively and be 70 microns, ion exchange capacity and be 45mmol/100g join in the 100g deionized water, 70 ℃ stir 5h down after, centrifugation, repeatedly washing, drying obtains Co
2+The exchange mica; With above-mentioned Co
2+The exchange mica is scattered in the 500g deionized water, adds 2.668g ATS (Ammonium thiosulphate) (18mmol) simultaneously, and stirring and dissolving obtains mica load C oS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 4h under the uviol lamp, and (irradiation wavelength 365nm, irradiation intensity are 3.0mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is dried under 70 ℃ of vacuum, and obtaining product is mica load C oS photochemical catalyst.
Embodiment 4
Present embodiment provides a kind of rectorite load SnS
2The preparation method of photochemical catalyst is to utilize photochemical method to prepare rectorite load SnS
2The method of photochemical catalyst, specifically undertaken by following step:
The rectorite and the 0.852g tin acetate (2.4mmol) that take by weighing the 8g average grain diameter respectively and be 65 microns, ion exchange capacity and be 30mmol/100g join in the 200g deionized water, 70 ℃ stir 4h down after, centrifugation, repeatedly washing, drying obtains Sn
4+The exchange rectorite; With above-mentioned Sn
4+The exchange rectorite is scattered in the 800g deionized water, adds 0.298g hypo (1.2mmol) simultaneously, and stirring and dissolving obtains rectorite load SnS
2Precursor liquid; The precursor aqueous solution that obtains is placed irradiation 12h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 3.8mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is dried under 70 ℃ of vacuum, and obtaining product is rectorite load SnS
2Photochemical catalyst.
Embodiment 5
Present embodiment provides a kind of preparation method of rectorite load NiS photochemical catalyst, is to utilize photochemical method to prepare the method for rectorite load NiS photochemical catalyst, is specifically undertaken by following step:
The rectorite and the 0.989g nickel nitrate (3.4mmol) that take by weighing the 10g average grain diameter respectively and be 75 microns, ion exchange capacity and be 34mmol/100g join in the 300g deionized water, 80 ℃ stir 2h down after, centrifugation, repeatedly washing, drying obtains Ni
2+The exchange rectorite; With above-mentioned Ni
2+The exchange rectorite is scattered in the 500g deionized water, adds 0.084g hypo (0.34mmol) simultaneously, and stirring and dissolving obtains rectorite load NiS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 4h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 4.2mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is dried under 90 ℃ of vacuum, and obtaining product is rectorite load NiS photochemical catalyst.
Embodiment 6
Present embodiment provides a kind of rectorite load Fe
2S
3The preparation method of photochemical catalyst is to utilize photochemical method to prepare rectorite load Fe
2S
3The method of photochemical catalyst, specifically undertaken by following step:
The rectorite and 1.297 Iron trichloride hexahydrates (4.8mmol) that take by weighing the 15g average grain diameter respectively and be 80 microns, ion exchange capacity and be 32mmol/100g join in the 500g deionized water, 70 ℃ stir 6h down after, centrifugation, repeatedly washing, drying obtains Fe
3+The exchange rectorite; With above-mentioned Fe
3+The exchange rectorite is scattered in the 150g deionized water, adds 0.449g five hydration potassium thiosulfates (1.6mmol) simultaneously, and stirring and dissolving obtains rectorite load Fe
2S
3Precursor liquid; The precursor aqueous solution that obtains is placed irradiation 24h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 0.5mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is dried under 60 ℃ of vacuum, and obtaining product is rectorite load Fe
2S
3Photochemical catalyst.
Embodiment 7
Present embodiment provides a kind of preparation method of calcium-base montmorillonite load ZnS photochemical catalyst, is to utilize photochemical method to prepare the method for phyllosilicate loaded ZnS photochemical catalyst, is specifically undertaken by following step:
The calcium-base montmorillonite and the 1.976g zinc acetate (9mmol) that take by weighing the 10g average grain diameter respectively and be 20 microns, ion exchange capacity and be 90mmol/100g join in the 250g deionized water, 60 ℃ stir 5h down after, centrifugation, repeatedly washing, drying obtains Zn
2+The exchange imvite; With above-mentioned Zn
2+The exchange imvite is scattered in the 200g deionized water, adds 0.248g hypo (1mmol) simultaneously, and stirring and dissolving obtains montmorillonite load ZnS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 10h under the uviol lamp, and (irradiation wavelength 365nm, irradiation intensity are 2.1mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is dried under 60 ℃ of vacuum, and obtaining product is montmorillonite load ZnS photochemical catalyst.
Embodiment 8
Present embodiment provides a kind of preparation method of sodium-based montmorillonite load C rS photochemical catalyst, is to utilize photochemical method to prepare the method for phyllosilicate load C rS photochemical catalyst, is specifically undertaken by following step:
The sodium-based montmorillonite and the 2.131g chromium chloride hexahydrate (8mmol) that take by weighing the 8g average grain diameter respectively and be 20 microns, ion exchange capacity and be 100mmol/100g join in the 150g deionized water, 70 ℃ stir 5h down after, centrifugation, repeatedly washing, drying obtains Cr
2+The exchange imvite; With above-mentioned Cr
2+The exchange imvite is scattered in the 200g deionized water, adds 2.371g ATS (Ammonium thiosulphate) (16mmol) simultaneously, and stirring and dissolving obtains montmorillonite load CrS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 32h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 1.8mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is dried under 85 ℃ of vacuum, and obtaining product is montmorillonite load CrS photochemical catalyst.
Embodiment 9
Present embodiment provides a kind of preparation method of attapulgite load P bS photochemical catalyst, is to utilize photochemical method to prepare the method for attapulgite load P bS photochemical catalyst, is specifically undertaken by following step:
The attapulgite and the 0.628g acetate trihydrate lead (2.6mmol) that take by weighing the 20g average grain diameter respectively and be 75 microns, ion exchange capacity and be 13mmol/100g join in the 500g deionized water, 50 ℃ stir 6h down after, centrifugation, repeatedly washing, drying obtains Pb
2+The exchange attapulgite; With above-mentioned Pb
2+The exchange attapulgite is scattered in the 450g deionized water, adds 3.872g hypo (15.6mmol) simultaneously, and stirring and dissolving obtains attapulgite load P bS precursor liquid; The precursor aqueous solution that obtains is placed irradiation 8h under the uviol lamp, and (irradiation wavelength 254nm, irradiation intensity are 4.5mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is dried under 90 ℃ of vacuum, and obtaining product is attapulgite load P bS photochemical catalyst.
Embodiment 10
Present embodiment provides a kind of mica loaded Ag
2The preparation method of S photochemical catalyst is to utilize photochemical method to prepare the mica loaded Ag
2The method of S photochemical catalyst, specifically undertaken by following step:
The mica and the 0.204g silver nitrate (1.2mmol) that take by weighing the 3g average grain diameter respectively and be 65 microns, ion exchange capacity and be 40mmol/100g join in the 100g deionized water, 50 ℃ stir 5h down after, centrifugation, repeatedly washing, drying obtains Ag
+The exchange mica; With above-mentioned Ag
+The exchange mica is scattered in the 100g deionized water, adds 0.815g hypo (4.8mmol) simultaneously, and stirring and dissolving obtains the mica loaded Ag
2The S precursor liquid; The precursor aqueous solution that obtains is placed irradiation 24 under the uviol lamp, and (irradiation wavelength 365nm, irradiation intensity are 2.5mW/cm
2); Product in the precursor aqueous solution reaction system behind the irradiation is filtered, repeatedly washs to neutrality with deionized water, and sample is dried under 60 ℃ of vacuum, and obtaining product is the mica loaded Ag
2The S photochemical catalyst.
The photochemical catalyst that makes below by the commercial P-25 photochemical catalyst of selecting German Deggusa company to produce and various embodiments of the present invention carries out the photocatalysis contrast experiment, and is specific as follows:
Photocatalysis experiment: urge agent to take by weighing 0.05g respectively P-25 and the prepared light of the various embodiments described above, the concentration that is scattered in 200ml is to form dispersion liquid in the methyl orange aqueous solution of 10mg/L, under room temperature, place dark to locate ultrasonic 10min dispersion liquid, after stirring the 10min clock then, change in the quartzy Photoreactor of column, respectively with the mercury lamp of 300W as ultraviolet source, with the 500W xenon lamp as visible light source, under magnetic agitation with the degradation rate of irradiation 1h as final degradation rate.If under natural daylight, carry out degradation reaction, then will be ultrasonic and stir after dispersion liquid pour in the 250ml beaker, under magnetic agitation, beaker placed under the sunshine direct sample mensuration degradation rate behind the irradiation 1h.The prepared phyllosilicate loaded metal sulphide photocatalytic degradation performance of each embodiment sees Table 1:
Table 1: photochemical catalyst is photocatalytic degradation methyl orange performance (degradation rate/hour) under different radiation sources
| Ultraviolet light | Visible light | Natural daylight | |
| P25 | 99.3 | 71.2 | 53.1 |
| Embodiment 1 | 93.2 | 70.4 | 53.6 |
| Embodiment 2 | 94.8 | 71.1 | 51.7 |
| Embodiment 3 | 91.7 | 69.8 | 50.8 |
| Embodiment 4 | 95.1 | 70.6 | 54.2 |
| Embodiment 5 | 93.8 | 68.7 | 51.8 |
| Embodiment 6 | 92.5 | 70.8 | 54.1 |
| Embodiment 7 | 96.2 | 71.6 | 50.6 |
| Embodiment 8 | 97.6 | 69.5 | 51.9 |
| Embodiment 9 | 95.4 | 70.3 | 49.3 |
| Embodiment 10 | 96.8 | 67.5 | 52.7 |
Annotate: degradation rate (%)=(methyl orange concentration behind the 1-irradiation/predose methyl orange concentration) * 100
As seen from table, the prepared photochemical catalyst of various embodiments of the present invention can be at natural daylight, ultraviolet light, and under the visible light degraded methyl orange is all had higher photocatalytic activity, be highly active photochemical catalyst.
In sum, the embodiment of the invention utilizes the photochemistry synthetic technology that a kind of method for preparing the phyllosilicate loaded metal sulphide photocatalyst product is provided, this method technology is simple, the reaction condition gentleness, is easy to control, cleaning and workable, the advantage that cost is low.
The above; only be the preferable specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; the present invention is not caused any restriction because of the succession of each embodiment yet; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (7)
1. the photochemical method for preparation of phyllosilicate loaded metal sulphide photocatalyst is characterized in that, this method may further comprise the steps:
(1) preparation metal ion exchanged phyllosilicate: phyllosilicate is scattered in the aqueous solution of metalline, stirred 2～6 hours down at 40～80 ℃, in swelling, carry out metal ion exchanged, phyllosilicate after the exchange is separated, washs, obtain the metal ion exchanged phyllosilicate;
(2) preparation precursor liquid: the described metal ion exchanged phyllosilicate that will make is distributed to the precursor liquid that is mixed with phyllosilicate loaded metal sulphide in the aqueous solution that contains the sulphur source;
(3) photochemical reaction: the precursor liquid of the phyllosilicate loaded metal sulphide that makes is positioned under the ultraviolet source stirring reaction 4～48 hours;
(4) post processing of photochemical catalyst: after photochemical reaction finishes, after filtration, promptly get phyllosilicate loaded metal sulphide photocatalyst after the washing, drying;
Metal in the described slaine is selected from copper, cobalt, nickel, every, chromium, zinc, lead, silver, tin and iron; Described sulphur source is the solubility thiosulfate.
2. method according to claim 1 is characterized in that,
Step (1) is specially:
Phyllosilicate is distributed in the deionized water, compound concentration is the laminar silicic acid salt suspensioning liquid of 1.0～100g/L, the ion exchange capacity of pressing phyllosilicate adds slaine, under 40～80 ℃ temperature, stirred 2～6 hours, in swelling, carry out ion-exchange, phyllosilicate after the exchange is separated, washs, obtain the metal ion exchanged phyllosilicate;
Step (2) is specially:
The above-mentioned metal ion exchanged phyllosilicate that makes is distributed in the deionized water, the consumption of deionized water is 10～100 times of phyllosilicate weight, add the sulphur source then, the sulphur source is (0.1～10) with the ratio of the amount of substance of slaine: 1, stirring and dissolving under room temperature obtains the precursor liquid of phyllosilicate loaded metal sulphide;
Step (3) is specially:
With the precursor liquid of the above-mentioned phyllosilicate loaded metal sulphide that makes be positioned under the ultraviolet source that wavelength is 254～365nm, irradiation intensity is 0.5～5.0mW/cm
2, stirring reaction 4～48 hours.
3. preparation method according to claim 1 and 2 is characterized in that, the described drying of step (4) is 60～90 ℃ of vacuum drying.
4. preparation method according to claim 1 and 2 is characterized in that layered silicate is selected from imvite, attapulgite, mica and rectorite.
5. preparation method according to claim 1 and 2 is characterized in that, the ion exchange capacity of layered silicate is that 15～110mmol/100g, particle diameter are 10～80 microns.
6. preparation method according to claim 1 and 2 is characterized in that described slaine is selected from chloride, acetate, nitrate and sulfate.
7. preparation method according to claim 1 is characterized in that, described thiosulfate is sodium thiosulfate, potassium thiosulfate or ATS (Ammonium thiosulphate).
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| CN110586133A (en) * | 2019-09-11 | 2019-12-20 | 天津大学 | Niobium acid-based sulfide composite material and preparation method thereof |
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| US20070253668A1 (en) * | 2004-12-08 | 2007-11-01 | Nanyang Technological University | Method of Producing Germanosilicate with a High Refractive Index Change |
| JP2007307540A (en) * | 2006-05-22 | 2007-11-29 | Ichiro Moriya | Photocatalyst showing high activity under exposure to white fluorescent lighting |
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| US20070253668A1 (en) * | 2004-12-08 | 2007-11-01 | Nanyang Technological University | Method of Producing Germanosilicate with a High Refractive Index Change |
| JP2007307540A (en) * | 2006-05-22 | 2007-11-29 | Ichiro Moriya | Photocatalyst showing high activity under exposure to white fluorescent lighting |
| CN101121124A (en) * | 2007-07-18 | 2008-02-13 | 淮阴师范学院 | Method for synthesizing attapulgite composite photocatalyst |
| CN101229510A (en) * | 2008-01-31 | 2008-07-30 | 福州大学 | Synthesis and applications of silicate containing Bi |
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